Method of manufacturing semiconductor device, substrate processing apparatus, and recording medium

ABSTRACT

There is provided a technique that includes: forming a first film to have a first predetermined film thickness over a substrate by performing a first cycle a first predetermined number of times, the first cycle including non-simultaneously performing: (a1) forming an oxynitride film by supplying a first film-forming gas to the substrate; and (a2) changing the oxynitride film into a first oxide film by supplying a first oxidizing gas to the substrate to oxidize the oxynitride film.

CROSS-REFERENCE TO RELATED APPLICATION

This application is continuation of U.S. patent application Ser. No.17/200,172, filed Mar. 12, 2021, which is based upon and claims thebenefit of priority from Japanese Patent Application No. 2020-052448,filed on Mar. 24, 2020, the entire contents of which are incorporatedherein by reference.

TECHNICAL FIELD

The present disclosure relates to a method of manufacturing asemiconductor device, a substrate processing apparatus, and a recordingmedium.

BACKGROUND

In the related art, as a process of manufacturing a semiconductordevice, an oxide film-forming process including formation of a nitridefilm over a substrate and change of the nitride film to an oxide film byoxidizing the nitride film may be often carried out.

SUMMARY

Some embodiments of the present disclosure provide a technique capableof improving a film quality of an oxide film formed over a substrate.

According to some embodiments of the present disclosure, there isprovided a technique that includes: forming a first film to have a firstpredetermined film thickness over a substrate by performing a firstcycle a first predetermined number of times, the first cycle includingnon-simultaneously performing: (a1) forming an oxynitride film bysupplying a first film-forming gas to the substrate; and (a2) changingthe oxynitride film into a first oxide film by supplying a firstoxidizing gas to the substrate to oxidize the oxynitride film.

BRIEF DESCRIPTION OF DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of the specification, illustrate embodiments of the presentdisclosure.

FIG. 1 is a schematic configuration view of a vertical process furnaceof a substrate processing apparatus suitably used in some embodiments ofthe present disclosure, in which a portion of the process furnace 202 isshown in a vertical cross-sectional view.

FIG. 2 is a schematic configuration view of the vertical process furnaceof the substrate processing apparatus suitably used in some embodimentsof the present disclosure, in which a portion of the process furnace 202is shown in a cross-sectional view taken along a line A-A in FIG. 1 .

FIG. 3 is a schematic configuration diagram of a controller 121 of thesubstrate processing apparatus suitably used in some embodiments of thepresent disclosure, in which a control system of the controller 121 isshown in a block diagram.

FIG. 4A is an enlarged partial cross-sectional view of a surface of awafer 200 after a silicon oxynitride film is formed with the surface ofthe wafer 200 as a base. FIG. 4B is an enlarged partial cross-sectionalview of the surface of the wafer 200 after the silicon oxynitride filmformed with the surface of the wafer 200 as the base is oxidized to bechanged into a silicon oxide film.

FIG. 4C is an enlarged partial cross-sectional view of the surface ofthe wafer 200 after a silicon oxynitride film is formed with the siliconoxide film, as a base, formed over the wafer 200 by oxidizing thesilicon oxynitride film. FIG. 4D is an enlarged partial cross-sectionalview of the surface of the wafer 200 after the silicon oxynitride filmformed with the silicon oxide film, as a base, formed over the wafer 200by oxidizing the silicon oxynitride film is oxidized to be changed intoa silicon oxide film.

FIG. 5A is an enlarged partial cross-sectional view of a surface of awafer 200 after a silicon nitride film is formed with the surface of thewafer 200 as a base. FIG. 5B is an enlarged partial cross-sectional viewof the surface of the wafer 200 after the silicon nitride film formedwith the surface of the wafer 200 as the base is oxidized to be changedinto a silicon oxide film. FIG. 5C is an enlarged partialcross-sectional view of the surface of the wafer 200 after a siliconoxynitride film is formed with the silicon oxide film, as a base, formedover the wafer 200 by oxidizing the silicon nitride film. FIG. 5D is anenlarged partial cross-sectional view of the surface of the wafer 200after the silicon oxynitride film formed with the silicon oxide film, asa base, formed over the wafer 200 by oxidizing the silicon nitride filmis oxidized to be changed into a silicon oxide film.

FIG. 6A is an enlarged partial cross-sectional view of a surface of awafer 200 after a silicon oxynitride film is formed with the surface ofthe wafer 200 as a base. FIG. 6B is an enlarged partial cross-sectionalview of the surface of the wafer 200 after the silicon oxynitride filmformed with the surface of the wafer 200 as the base is oxidized to bechanged into a silicon oxide film.

FIG. 6C is an enlarged partial cross-sectional view of the surface ofthe wafer 200 after a silicon nitride film is formed with the siliconoxide film, as a base, formed over the wafer 200 by oxidizing thesilicon oxynitride film. FIG. 6D is an enlarged partial cross-sectionalview of the surface of the wafer 200 after the silicon nitride filmformed with the silicon oxide film, as a base, formed over the wafer 200by oxidizing the silicon oxynitride film is oxidized to be changed intoa silicon oxide film.

FIG. 7A is a diagram showing measurement results of film thicknesses ofa silicon oxynitride film formed over a wafer and a silicon oxide filmobtained by oxidizing the silicon oxynitride film. FIG. 7B is a diagramshowing measurement results of film stresses in a silicon oxynitridefilm formed over a wafer and a silicon oxide film obtained by oxidizingthe silicon oxynitride film.

FIG. 8A is a diagram showing measurement results of film thicknesses ofa silicon nitride film formed over a wafer and a silicon oxide filmobtained by oxidizing the silicon nitride film.

FIG. 8B is a diagram showing measurement results of stresses in asilicon nitride film formed over a wafer and a silicon oxide filmobtained by oxidizing the silicon nitride film.

DETAILED DESCRIPTION Embodiments of the Present Disclosure

Some embodiments of the present disclosure will be now described mainlywith reference to FIGS. 1 to 4D.

(1) Configuration of Substrate Processing Apparatus

As illustrated in FIG. 1 , a process furnace 202 includes a heater 207as a temperature regulator (heating part). The heater 207 has acylindrical shape and is supported by a holding plate to be verticallyinstalled. The heater 207 functions as an activation mechanism (anexcitation part) configured to thermally activate (excite) a gas.

A reaction tube 203 is disposed inside the heater 207 to be concentricwith the heater 207. The reaction tube 203 is made of a heat resistantmaterial, for example, quartz (SiO₂), silicon carbide (SiC) or the like,and has a cylindrical shape with its upper end closed and its lower endopened. A manifold 209 is disposed below the reaction tube 203 in aconcentric relationship with the reaction tube 203. The manifold 209 ismade of a metal material, for example, stainless steel (SUS), and has acylindrical shape with its upper and lower ends opened. The upper end ofthe manifold 209 engages with the lower end of the reaction tube 203.The manifold 209 is configured to support the reaction tube 203. AnO-ring 220 a as a seal member is installed between the manifold 209 andthe reaction tube 203. Similar to the heater 207, the reaction tube 203is vertically installed. A processing vessel (reaction vessel) mainlyincludes the reaction tube 203 and the manifold 209. A process chamber201 is formed in a hollow cylindrical portion of the processing vessel.The process chamber 201 is configured to be capable of accommodatingwafers 200 as substrates. The processing of the wafers 200 is performedin the process chamber 201.

Nozzles 249 a to 249 c as first to third supply parts are installed inthe process chamber 201 to penetrate a sidewall of the manifold 209. Thenozzles 249 a to 249 c will be referred to as first to third nozzles,respectively. The nozzles 249 a to 249 c are each made of a heatresistant material such as quartz, SiC or the like. Gas supply pipes 232a to 232 c are connected to the nozzles 249 a to 249 c respectively. Thenozzles 249 a to 249 c are different nozzles, and each of the nozzles249 a to 249 c is installed adjacent to the nozzle 249 b.

Mass flow controllers (MFCs) 241 a to 241 c, which are flow ratecontrollers (flow rate control parts), and valves 243 a to 243 c, whichare opening/closing valves, are installed at the gas supply pipes 232 ato 232 c sequentially from the corresponding upstream sides of gas flow,respectively. Gas supply pipes 232 d and 232 f are respectivelyconnected to the gas supply pipe 232 a at the downstream side of thevalve 243 a. Gas supply pipes 232 e and 232 g are respectively connectedto the gas supply pipe 232 b at the downstream side of the valve 243 b.A gas supply pipe 232 h is connected to the gas supply pipe 232 c at thedownstream side of the valve 243 c. MFCs 241 d to 241 h and valves 243 dto 243 h are installed at the gas supply pipes 232 d to 232 hsequentially from the corresponding upstream sides of gas flow,respectively. The gas supply pipes 232 a to 232 h are each made of ametal material such as stainless steel (SUS) or the like.

As illustrated in FIG. 2 , the nozzles 249 a to 249 c are disposed in aspace with an annular plane-view shape between the inner wall of thereaction tube 203 and the wafers 200 such that the nozzles 249 a to 249c extend upward along an arrangement direction of the wafers 200 from alower portion to an upper portion of the inner wall of the reaction tube203. Specifically, the nozzles 249 a to 249 c are installed at a lateralside of a wafer arrangement region in which the wafers 200 are arranged,namely in a region which horizontally surrounds the wafer arrangementregion, to extend along the wafer arrangement region. The nozzle 249 bis disposed to face an exhaust port 231 a, which is described below, ona straight line in a plane view, with centers of the wafers 200 loadedinto the process chamber 201 interposed therebetween. The nozzles 249 aand 249 c are disposed to sandwich a straight line L passing through thenozzle 249 b and a center of the exhaust port 231 a from both sidesalong the inner wall of the reaction tube 203 (an outer peripheralportion of the wafers 200). The straight line L is also a straight linepassing through the nozzle 249 b and the centers of the wafers 200. Thatis, it may be said that the nozzle 249 c is installed at the oppositeside of the nozzle 249 a with the straight line L interposedtherebetween. The nozzles 249 a and 249 c are disposed in line symmetrywith the straight line L as a symmetry axis. Gas supply holes 250 a to250 c configured to supply a gas are installed at the side surfaces ofthe nozzles 249 a to 249 c, respectively. The gas supply holes 250 a to250 c are opened to face the exhaust port 231 a in the plane view, thusallowing a gas to be supplied toward the wafers 200. The gas supplyholes 250 a to 250 c may be formed in a plural number between the lowerportion and the upper portion of the reaction tube 203.

A precursor (precursor gas), for example, a silane-based gas whichcontains silicon (Si) as a main element constituting a film to be formedover each of the wafers 200, is supplied from the gas supply pipe 232 ainto the process chamber 201 via the MFC 241 a, the valve 243 a, and thenozzle 249 a. As the silane-based gas, it may be possible to use, forexample, a gas containing Si and halogen, that is, a halosilane-basedgas. The halogen includes chlorine (Cl), fluorine (F), bromine (Br),iodine (I), and the like. As the halosilane-based gas, it may bepossible to use, for example, a chlorosilane-based gas containing Si andCl.

A nitriding gas (nitriding agent), for example, a nitrogen (N)- andhydrogen (H)-containing gas, is supplied from the gas supply pipe 232 binto the process chamber 201 via the MFC 241 b, the valve 243 b, and thenozzle 249 b. The N- and H-containing gas is both a N-containing gas anda H-containing gas.

An oxidizing gas (oxidizing agent), for example, an oxygen(O)-containing gas, is supplied from the gas supply pipe 232 c into theprocess chamber 201 via the MFC 241 c, the valve 243 c, and the nozzle249 c.

A precursor (precursor gas), for example, a silane-based gas whichcontains Si as a main element constituting a film to be formed over eachof the wafers 200, is supplied from the gas supply pipe 232 d into theprocess chamber 201 via the MFC 241 d, the valve 243 d, the gas supplypipe 232 a, and the nozzle 249 a. As the silane-based gas, it may bepossible to use, for example, a gas containing Si and halogen, that is,a halosilane-based gas. As the halosilane-based gas, it may be possibleto use, for example, a chlorosilane-based gas containing Si and Cl.

A reducing gas (reducing agent), for example, a hydrogen (H)-containinggas, is supplied from the gas supply pipe 232 e into the process chamber201 via the MFC 241 e, the valve 243 e, the gas supply pipe 232 b, andthe nozzle 249 b. The H-containing gas alone does not obtain anoxidation action, but it reacts with an O-containing gas under aspecific condition to generate oxidation species such as atomic oxygen(O) or the like and acts to improve an efficiency of oxidizing reaction.

An inert gas is supplied from the gas supply pipes 232 f to 232 h intothe process chamber 201 via the MFCs 241 f to 241 h, the valves 243 f to243 h, the gas supply pipes 232 a to 232 c, and the nozzles 249 a to 249c, respectively. The inert gas acts as a purge gas, a carrier gas, adilution gas, or the like.

A precursor gas supply system (first precursor gas supply system) mainlyincludes the gas supply pipe 232 a, the MFC 241 a, and the valve 243 a.A nitriding gas supply system (N- and H-containing supply system) mainlyincludes the gas supply pipe 232 b, the MFC 241 b, and the valve 243 b.An oxidizing gas supply system (O-containing gas supply system) mainlyincludes the gas supply pipe 232 c, the MFC 241 c, and the valve 243 c.A precursor gas supply system (second precursor gas supply system)mainly includes the gas supply pipe 232 d, the MFC 241 d, and the valve243 d. A reducing gas supply system (H-containing gas supply system)mainly includes the gas supply pipe 232 e, the MFC 241 e, and the valve243 e. An inert gas supply system mainly includes the gas supply pipes232 f to 232 h, the MFCs 241 f to 241 h, and the valves 243 f to 243 h.

Each or all of the precursor gases, the N- and H-containing gas, and theO-containing gas will be also referred to as a film-forming gas, andeach or all of the precursor gas supply system, the N- and H-containinggas supply system, and the O-containing gas supply system will be alsoreferred to as a film-forming gas supply system. Further, each or bothof the O-containing gas and the H-containing gas will be also referredto as an oxidizing gas, and each or both of the O-containing gas supplysystem and the H-containing gas supply system will be also referred toas an oxidizing gas supply system.

One or all of the various gas supply systems described above may beconfigured as an integrated gas supply system 248 in which the valves243 a to 243 h, the MFCs 241 a to 241 h, and the like are integrated.The integrated gas supply system 248 is connected to each of the gassupply pipes 232 a to 232 h so that a supply operation of various gasesinto the gas supply pipes 232 a to 232 h, that is, an opening/closingoperation of the valves 243 a to 243 h, a flow rate regulating operationby the MFCs 241 a to 241 h, and the like, is controlled by a controller121 to be described below. The integrated gas supply system 248 isconfigured as an integral or dividable integrated unit, and may beattached to or detached from the gas supply pipes 232 a to 232 h and thelike on an integrated unit basis, such that maintenance, replacement,extension, and the like of the integrated gas supply system 248 may beperformed on the integrated unit basis.

The exhaust port 231 a configured to exhaust an internal atmosphere ofthe process chamber 201 is installed at a lower side of the sidewall ofthe reaction tube 203. As illustrated in FIG. 2 , the exhaust port 231 ais installed at a position facing the nozzles 249 a to 249 c (the gassupply holes 250 a to 250 c) in the plane view, with the wafers 200interposed therebetween. The exhaust port 231 a may be installed betweenthe lower portion and the upper portion of the sidewall of the reactiontube 203, that is, along the wafer arrangement region. An exhaust pipe231 is connected to the exhaust port 231 a. A vacuum pump 246 as avacuum exhaust device is connected to the exhaust pipe 231 via apressure sensor 245 as a pressure detector (pressure detection part)which detects the internal pressure of the process chamber 201 and anauto pressure controller (APC) valve 244 as a pressure regulator(pressure regulation part). The APC valve 244 is configured so that avacuum exhaust and a vacuum exhaust stop of the interior of the processchamber 201 can be performed by opening and closing the APC valve 244while operating the vacuum pump 246 and so that the internal pressure ofthe process chamber 201 can be regulated by adjusting an opening degreeof the APC valve 244 based on pressure information detected by thepressure sensor 245 while operating the vacuum pump 246. An exhaustsystem mainly includes the exhaust pipe 231, the APC valve 244 and thepressure sensor 245. The vacuum pump 246 may be regarded as beingincluded in the exhaust system.

A seal cap 219, which serves as a furnace opening lid configured to becapable of hermetically sealing a lower end opening of the manifold 209,is installed under the manifold 209. The seal cap 219 is made of a metalmaterial such as stainless steel (SUS) or the like, and is formed in adisc shape. An O-ring 220 b, which is a seal member making contact withthe lower end portion of the manifold 209, is installed on an uppersurface of the seal cap 219. A rotation mechanism 267 configured torotate a boat 217 to be described below is installed under the seal cap219. A rotary shaft 255 of the rotation mechanism 267, which penetratesthe seal cap 219, is connected to the boat 217. The rotation mechanism267 is configured to rotate the wafers 200 by rotating the boat 217. Theseal cap 219 is configured to be vertically moved up or down by a boatelevator 115 which is an elevator mechanism installed outside thereaction tube 203. The boat elevator 115 is configured as a transferdevice (transfer mechanism) which loads and unloads (transfers) thewafers 200 into and from (out of) the process chamber 201 by moving theseal cap 219 up or down.

A shutter 219 s as a furnace opening lid capable of hermetically sealingthe lower end opening of the manifold 209, with the boat 217 unloadedfrom the interior of the process chamber 201 by moving the seal cap 219down, is installed under the manifold 209. The shutter 219 s is made ofa metal material such as stainless steel or the like, and is formed in adisc shape. An O-ring 220 c as a seal member making contact with thelower end portion of the manifold 209 is installed on an upper surfaceof the shutter 219 s. An opening/closing operation (an elevationmovement operation or a rotational movement operation) of the shutter219 s is controlled by a shutter opening/closing mechanism 115 s.

The boat 217 serving as a substrate support is configured to support aplurality of wafers 200, for example, 25 to 200 wafers, in such a statethat the wafers 200 are arranged in a horizontal posture and in multiplestages along a vertical direction with the centers of the wafers 200aligned with one another. That is, the boat 217 is configured to arrangethe wafers 200 to be spaced apart from each other. The boat 217 is madeof a heat resistant material such as quartz or SiC. Heat insulatingplates 218 made of a heat resistant material such as quartz or SiC areinstalled below the boat 217 in multiple stages.

A temperature sensor 263 serving as a temperature detector is installedin the reaction tube 203. Based on temperature information detected bythe temperature sensor 263, a state of supplying electric power to theheater 207 is regulated such that the interior of the process chamber201 has a desired temperature distribution. The temperature sensor 263is installed along the inner wall of the reaction tube 203.

As illustrated in FIG. 3 , the controller 121, which is a control part(control means), may be configured as a computer including a centralprocessing unit (CPU) 121 a, a random access memory (RAM) 121 b, amemory 121 c, and an I/O port 121 d. The RAM 121 b, the memory 121 c andthe I/O port 121 d are configured to be capable of exchanging data withthe CPU 121 a via an internal bus 121 e. An input/output device 122configured as, for example, a touch panel or the like, is connected tothe controller 121.

The memory 121 c includes, for example, a flash memory, a hard diskdrive (HDD), a solid state drive (SSD), and the like. A control programthat controls operations of a substrate processing apparatus, a processrecipe in which sequences, conditions, and the like of substrateprocessing to be described below are described, and the like arereadably stored in the memory 121 c. The process recipe functions as aprogram configured to be capable of causing the controller 121 toexecute each sequence in the substrate processing to be described laterto obtain a predetermined result. Hereinafter, the process recipe andthe control program will be generally and simply referred to as a“program.” Further, the process recipe will be simply referred to as a“recipe.” When the term “program” is used herein, it may indicate a caseof including only the recipe, a case of including only the controlprogram, or a case of including both the recipe and the control program.The RAM 121 b is configured as a memory area (work area) in which aprogram, data, and the like read by the CPU 121 a is temporarily stored.

The I/O port 121 d is connected to the MFCs 241 a to 241 f, the valves243 a to 243 f, the pressure sensor 245, the APC valve 244, the vacuumpump 246, the temperature sensor 263, the heater 207, the rotationmechanism 267, the boat elevator 115, the shutter opening/closingmechanism 115 s, and the like, as described above.

The CPU 121 a is configured to read the control program from the memory121 c and execute the same. The CPU 121 a also reads the recipe from thememory 121 c according to an input of an operation command from theinput/output device 122, and the like. In addition, the CPU 121 a isconfigured to control, according to the contents of the recipe thusread, the flow rate regulating operation of various types of gases bythe MFCs 241 a to 241 f, the opening/closing operation of the valves 243a to 243 f, the opening/closing operation of the APC valve 244, thepressure regulating operation performed by the APC valve 244 based onthe pressure sensor 245, the driving and stopping of the vacuum pump246, the temperature regulating operation performed by the heater 207based on the temperature sensor 263, the operation of rotating the boat217 and adjusting the rotation speed of the boat 217 with the rotationmechanism 267, the operation of moving the boat 217 up or down with theboat elevator 115, the operation of opening and closing the shutter 219s with the shutter opening/closing mechanism 115 s, and the like.

The controller 121 may be configured by installing, on the computer, theaforementioned program stored in an external memory 123. The externalmemory 123 may include, for example, a magnetic disc such as a HDD, anoptical disc such as a CD, a magneto-optical disc such as a MO, asemiconductor memory such as a USB memory and a SSD, and the like. Thememory 121 c or the external memory 123 is configured as acomputer-readable recording medium. Hereinafter, the memory 121 c andthe external memory 123 will be generally and simply referred to as a“recording medium.” When the term “recording medium” is used herein, itmay indicate a case of including only the memory 121 c, a case ofincluding only the external memory 123, or a case of including both thememory 121 c and the external memory 123. Further, the program may besupplied to the computer by using a communication means such as theInternet or a dedicated line, instead of using the external memory 23.

(2) Substrate Processing Process

A processing sequence example of forming an oxide film having apredetermined thickness over a wafer 200 as a substrate by using theaforementioned substrate processing apparatus, which is a process formanufacturing a semiconductor device, will be described mainly withreference to FIGS. 4A to 4D. In the following descriptions, theoperations of the respective parts constituting the substrate processingapparatus are controlled by the controller 121.

In a processing sequence according to some embodiments, a SiO filmhaving a predetermined film thickness is formed over a surface of awafer 200 by performing a cycle a predetermined number of times (n₂times, where n₂ is an integer of 1 or more), specifically a plurality oftimes (n₂ times, where n₂ is an integer of 2 or more) in someembodiments, the cycle including non-simultaneously performing:

-   -   a step of forming a silicon oxynitride film (SiON film) as an        oxynitride film by supplying a chlorosilane-based gas which is a        precursor gas, a N- and H-containing gas which is a nitriding        gas, and an O-containing gas which is an oxidizing gas, as        film-forming gases, to the wafer 200 (SiON film formation); and    -   a step of changing the SiON film into a silicon oxide film (SiO        film) as an oxide film by supplying an O-containing gas and a        H-containing gas, as oxidizing gases, to the wafer 200 to        oxidize the SiON film (SiO film change).

In the present disclosure, for the sake of convenience, theabove-described processing sequence may be denoted as follows. The samedenotation may be used in modifications to be described below. Inaddition, in the following description, “SiON” denotes “SiON filmformation,” and “Ox” denotes change from a SiON film into a SiO film byoxidation, that is, “SiO film change.”

(SiON→Ox)×n ₂⇒SiO

Further, in the processing sequence according to some embodiments, theSiON film formation includes performing a set a predetermined number oftimes (n₁ times, where n₁ is an integer of 1 or more), the setincluding: a step of supplying a chlorosilane-based gas to the wafer200; a step of supplying a N- and H-containing gas to the wafer 200; anda step of supplying an O-containing gas to the wafer 200.

Further, in the processing sequence according to some embodiments, theSiO film change includes supplying an O-containing gas and aH-containing gas simultaneously to the wafer 200.

In the present disclosure, for the sake of convenience, theabove-described gas supplying sequence may be denoted as follows. Thesame denotation may be used in modifications to be described below.

[(Chlorosilane-based gas→N- and H-containing gas→O-containing gas)×n₁→O-containing gas+H-containing gas]×n ₂⇒SiO

When the term “wafer” is used in the present disclosure, it may refer to“a wafer itself” or “a wafer and a stacked body of certain layers orfilms formed over a surface of the wafer.” When the phrase “a surface ofa wafer” is used in the present disclosure, it may refer to “a surfaceof a wafer itself” or “a surface of a certain layer or the like formedover a wafer.” When the expression “a certain layer is formed over awafer” is used in the present disclosure, it may mean that “a certainlayer is formed directly over a surface of a wafer itself” or that “acertain layer is formed over a layer or the like formed over a wafer.”When the term “substrate” is used in the present disclosure, it may besynonymous with the term “wafer.”

(Wafer Charging and Boat Loading)

After the boat 217 is charged with a plurality of wafers 200 (wafercharging), the shutter 219 s is moved by the shutter opening/closingmechanism 115 s to open the lower end opening of the manifold 209(shutter open). Thereafter, as illustrated in FIG. 1 , the boat 217charged with the plurality of wafers 200 is lifted up by the boatelevator 115 to be loaded into the process chamber 201 (boat loading).In this state, the seal cap 219 seals the lower end of the manifold 209via the O-ring 220 b.

(Pressure Regulation and Temperature Regulation)

After the boat loading is completed, the interior of the process chamber201, that is, a space where the wafers 200 are placed, isvacuum-exhausted (decompression-exhausted) by the vacuum pump 246 toreach a desired pressure (degree of vacuum). At this time, the internalpressure of the process chamber 201 is measured by the pressure sensor245, and the APC valve 244 is feedback-controlled based on the measuredpressure information (pressure regulation). Further, the wafers 200 inthe process chamber 201 are heated by the heater 207 to have a desiredprocessing temperature. At this time, a state of supplying electricpower to the heater 207 is feedback-controlled based on the temperatureinformation detected by the temperature sensor 263 so that the interiorof the process chamber 201 has a desired temperature distribution(temperature regulation). Further, the rotation of the wafers 200 by therotation mechanism 267 is started. The exhaust of the interior of theprocess chamber 201 and the heating and rotation of the wafers 200 arecontinuously performed at least until the processing on the wafers 200is completed.

(Film-Forming Process)

Then, a cycle including non-simultaneously performing: a step of forminga SiON film (SiON film formation); and a step of changing the SiON filminto a SiO film by oxidizing the SiON film (SiO film change) isperformed a plurality of times (n₂ times, where n₂ is an integer of 2 ormore).

(SiON Film Formation)

In the SiON film formation, a set in which the following steps 1 to 3are sequentially performed is performed a predetermined number of times(n₁ times, where n₁ is an integer of 1 or more).

[Step S1]

In the step S1, a chlorosilane-based gas is supplied to the wafer 200 inthe process chamber 201.

Specifically, the valve 243 a is opened to allow the chlorosilane-basedgas to flow through the gas supply pipe 232 a. A flow rate of thechlorosilane-based gas is regulated by the MFC 241 a, and thechlorosilane-based gas is supplied into the process chamber 201 via thenozzle 249 a and is exhausted via the exhaust port 231 a. In thisoperation, the chlorosilane-based gas is supplied to the wafer 200(chlorosilane-based gas supply). At this time, the valves 243 f to 243 hmay be opened to allow an inert gas to be supplied into the processchamber 201 via the nozzles 249 a to 249 c respectively.

Process conditions in this step are exemplified as follows.

-   -   Chlorosilane-based gas supply flow rate: 0.01 to 2 slm,        specifically 0.1 to 1 slm in some embodiments    -   Inert gas supply flow rate (for each gas supply pipe): 0 to 10        slm    -   Each gas supply time: 1 to 120 seconds, specifically 1 to 60        seconds in some embodiments    -   Processing temperature: 400 to 800 degrees C., specifically 600        to 700 degrees C. in some embodiments    -   Processing pressure: 1 to 2,666 Pa, specifically 67 to 1,333 Pa        in some embodiments

In the present disclosure, a notation of a numerical range such as “1 to2,666 Pa” means that a lower limit value and an upper limit value areincluded in the range. For example, “1 to 2,666 Pa” means “1 Pa or moreand 2,666 Pa or less”. The same applies to other numerical ranges.

By supplying the chlorosilane-based gas to the wafer 200 under theabove-mentioned conditions, a Si-containing layer containing Cl isformed over the outermost surface of the wafer 200 as a base. TheSi-containing layer containing Cl is formed by physical adsorption orchemical adsorption of molecules of the chlorosilane-based gas, chemicaladsorption of molecules of substance obtained when a portion of thechlorosilane-based gas is decomposed, deposition of Si by thermaldecomposition of the chlorosilane-based gas, and the like over theoutermost surface of the wafer 200. The Si-containing layer containingCl may be an adsorption layer (physical adsorption layer or chemicaladsorption layer) of molecules of the chlorosilane-based gas ormolecules of substance obtained when a portion of the chlorosilane-basedgas is decomposed or may be a deposition layer of Si containing Cl. Inthe present disclosure, the Si-containing layer containing Cl is alsosimply referred to as a Si-containing layer.

After the Si-containing layer is formed, the valve 243 a is closed tostop the supply of the chlorosilane-based gas into the process chamber201. Then, the interior of the process chamber 201 is vacuum-exhaustedto remove a gas and the like remaining in the process chamber 201 fromthe interior of the process chamber 201 (purge). At this time, thevalves 243 f to 243 h are opened to allow an inert gas to be suppliedinto the process chamber 201. The inert gas acts as a purge gas.

As the chlorosilane-based gas, it may be possible to use amonochlorosilane (SiH₃Cl, abbreviation: MCS) gas, a dichlorosilane(SiH₂Cl₂, abbreviation: DCS) gas, a trichlorosilane (SiHCl₃,abbreviation: TCS) gas, a tetrachlorosilane (SiCl₄, abbreviation: STC)gas, a hexachlorodisilane (Si₂Cl₆, abbreviation: HCDS) gas, anoctachlorotrisilane (Si₃Cl₈, abbreviation: OCTS) gas, or the like.Further, instead of the chlorosilane-based gas, it may also be possibleto use a fluorosilane-based gas such as a tetrafluorosilane (SiF₄) gas,a bromosilane-based gas such as a tetrabromosilane (SiBr₄) gas, or aniodosilane-based gas such as a tetraiodosilane (SiI₄) gas.

As the inert gas, it may be possible to use a N₂ gas or a rare gas suchas an Ar gas, a He gas, a Ne gas, or a Xe gas. The same applies to eachstep to be described later.

[Step S2]

After the step S1 is completed, a N- and H-containing gas is supplied tothe wafer 200 in the process chamber 201, that is, the Si-containinglayer formed over the wafer 200.

Specifically, the valve 243 b is opened to allow the N- and H-containinggas to flow through the gas supply pipe 232 b. A flow rate of the N- andH-containing gas is adjusted by the MFC 241 b, and the N- andH-containing gas is supplied into the process chamber 201 via the nozzle249 b and is exhausted via the exhaust port 231 a. In this operation,the N- and H-containing gas is supplied to the wafer 200 (N- andH-containing gas supply). At this time, the valves 243 f to 243 h may beopened to allow an inert gas to be supplied into the process chamber 201via of the nozzles 249 a to 249 c respectively.

Process conditions in this step are exemplified as follows.

-   -   N- and H-containing gas supply flow rate: 0.1 to 10 slm    -   N- and H-containing gas supply time: 1 to 120 seconds,        specifically 1 to 60 seconds in some embodiments    -   Processing pressure: 1 to 4,000 Pa, specifically 1 to 3,000 Pa        in some embodiments    -   Other process conditions are the same as the process conditions        in the step S1.

By supplying the N- and H-containing gas to the wafer 200 under theabove-mentioned conditions, at least a portion of the Si-containinglayer formed over the wafer 200 is nitrided (modified). As a result, asilicon nitride layer (SiN layer) is formed as a layer containing Si andN over the outermost surface of the wafer 200 as a base. When the SiNlayer is formed, impurities such as Cl contained in the Si-containinglayer constitute gaseous substance containing at least Cl in the processof modifying the Si-containing layer with the N- and H-containing gasand are discharged from the process chamber 201. As a result, the SiNlayer has fewer impurities such as Cl than those contained in theSi-containing layer formed in the step S1.

After the SiN layer is formed, the valve 243 b is closed to stop thesupply of the N- and H-containing gas into the process chamber 201.Then, according to the same process procedures as the purge in the stepS1, a gas and the like remaining in the process chamber 201 are removedfrom the process chamber 201 (purge).

As the N- and H-containing gas, it may be possible to use a hydrogennitride-based gas such as an ammonia (NH₃) gas, a diazene (N₂H₂) gas, ahydrazine (N₂H₄) gas, or a N₃H₈ gas.

[Step S3]

After the step S2 is completed, an O-containing gas is supplied to thewafer 200 in the process chamber 201, that is, the SiN layer formed overthe wafer 200.

Specifically, the valve 243 c is opened to allow the O-containing gas toflow through the gas supply pipe 232 c. A flow rate of the O-containinggas is regulated by the MFC 241 c, and the O-containing gas is suppliedinto the process chamber 201 via the nozzle 249 c and is exhausted viathe exhaust port 231 a. In this operation, the O-containing gas issupplied to the wafer 200 (O-containing gas supply). At this time, thevalves 243 f to 243 h may be opened to allow an inert gas to be suppliedinto the process chamber 201 via the nozzles 249 a to 249 crespectively.

Process conditions in this step are exemplified as follows.

-   -   O-containing gas supply flow rate: 0.1 to 10 slm    -   O-containing gas supply time: 1 to 120 seconds, specifically 1        to 60 seconds in some embodiments    -   Processing pressure: 1 to 4,000 Pa, specifically 1 to 3,000 Pa        in some embodiments    -   Other process conditions are the same as the process conditions        in the step S1.

By supplying the O-containing gas to the wafer 200 under theabove-mentioned conditions, at least a portion of the SiN layer formedover the wafer 200 is oxidized (modified). As a result, a siliconoxynitride layer (SiON layer) is formed as a layer containing Si, O, andN over the outermost surface of the wafer 200 as the base. When the SiONlayer is formed, impurities such as Cl contained in the SiN layerconstitute gaseous substance containing at least Cl in the process ofmodifying the SiN layer with the O-containing gas and are dischargedfrom the process chamber 201. As a result, the SiON layer has fewerimpurities such as Cl than those contained in the SiN layer formed inthe step S2.

After the SiON layer is formed, the valve 243 c is closed to stop thesupply of the O-containing gas into the process chamber 201. Then,according to the same process procedures as the purge in the step S1, agas and the like remaining in the process chamber 201 are removed fromthe process chamber 201 (purge).

As the O-containing gas, it may be possible to use an oxygen (O₂) gas,an ozone (O₃) gas, water vapor (H₂O gas), a hydrogen peroxide (H₂O₂)gas, a nitrous oxide (N₂O) gas, a nitric oxide (NO) gas, a nitrogendioxide. (NO₂) gas, a carbon monoxide (CO) gas, a carbon dioxide (CO₂)gas, or the like.

[Performing Set Predetermined Number of Times]

By performing a set a predetermined number of times (n₁ time, where n₁is an integer of 1 or more), the set including non-simultaneously, thatis, without synchronization, performing the steps S1 to S3 describedabove, a SiON film having a predetermined thickness may be formed overthe surface of the wafer 200 as a base, as illustrated in FIG. 4A. Theabove-described cycle may be performed a plurality of times. That is,the thickness of the SiON layer formed per cycle may be set to besmaller than a desired film thickness, and the above-described cycle maybe performed a plurality of times until the thickness of a SiON filmformed by stacking SiON layers reaches the desired film thickness.

Further, by performing this step under the above-mentioned processconditions, the SiON film formed over the wafer 200 becomes a filmhaving a relatively large stress, for example, a tensile stress having amagnitude of about 0.4 to 0.5 GPa.

[SiO Film Change]

After the SiON film having the predetermined thickness is formed, anO-containing gas and a H-containing gas are supplied to the wafer 200 inthe process chamber 201, that is, the SiON film formed over the wafer200.

Specifically, the valves 243 c and 243 e are opened to allow theO-containing gas and the H-containing gas to flow through the gas supplypipes 232 c and 232 e respectively. Flow rates of the O-containing gasand the H-containing gas flowing through the gas supply pipes 232 c and232 e are regulated by the MFCs 241 c and 241 e, respectively, and theO-containing gas and the H-containing gas are supplied into the processchamber 201 via the nozzles 249 c and 249 b, respectively. TheO-containing gas and the H-containing gas are mixed and react with eachother in the process chamber 201 and are then exhausted via the exhaustport 231 a. In this operation, water (H₂O)-free oxidizing speciescontaining oxygen such as atomic oxygen generated by the reactionbetween the O-containing gas and the H-containing gas are supplied tothe wafer 200 (O-containing gas+H-containing gas). At this time, thevalves 243 f to 243 h may be opened to allow an inert gas to be suppliedinto the process chamber 201 via the nozzles 249 a to 249 c.

Process conditions in this step are exemplified as follows.

-   -   O-containing gas supply flow rate: 0.1 to 10 slm    -   H-containing gas supply flow rate: 0.1 to 10 slm    -   Each gas supply time: 1 to 120 seconds, specifically 1 to 60        seconds in some embodiments    -   Processing pressure: 1 to 2,000 Pa, specifically 1 to 1,000 Pa        in some embodiments    -   Other process conditions are the same as the process conditions        in the step S1.

By supplying the O-containing gas and the H-containing gas to the wafer200 under the above-mentioned conditions, it is possible to furtherintroduce O into the SiON film by oxidizing the SiON film formed overthe wafer 200 by using a strong oxidizing power of the oxidizing speciessuch as atomic oxygen. Further, it is possible to desorb N contained inthe SiON film from the SiON film. As a result, as illustrated in FIG.4B, it is possible to change the SiON film formed over the wafer 200 inthe SiON film formation into the SiO film. The SiO film obtained byoxidizing the SiON film is a high-purity and dense SiO film containinglittle or no N.

Further, the SiON film expands by introducing O when it is changed intothe SiO film by the oxidation. Therefore, the SiO film obtained byoxidizing the SiON film becomes thicker than the SiON film before theoxidation. However, a degree of expansion (an expansion coefficient) ofthe film before and after the oxidation is smaller than a degree ofexpansion (an expansion coefficient) of the film before and after theoxidation when the set including the step of supplying thechlorosilane-based gas to the wafer 200 and the step of supplying the N-and H-containing gas to the wafer 200 is performed a predeterminednumber of times to form the silicon nitride film (SiN film) over thewafer 200 and the SiN film is oxidized to be changed into the SiO film.As illustrated in FIG. 7A, the present disclosers confirmed that thefilm thickness of the SiO film obtained by oxidizing the SiON film mayfall within about 1.3 times the film thickness of the SiON film beforethe oxidation. On the other hand, as illustrated in FIG. 8A, the presentdisclosers confirmed that the film thickness of the SiO film obtained byoxidizing the SiN film may increase to about 1.8 times the filmthickness of the SiN film before the oxidation. From this point, byusing the SiON film as a base film, it is possible to lower theexpansion coefficient of the SiO film obtained by oxidizing the basefilm, as compared with a case where the base film is the SiN film.

Further, a stress (membrane stress, internal stress, or residual stress)of the SiO film obtained by oxidizing the SiON film is smaller than astress of the SiON film before the oxidation. This stress is smallerthan the stress of the SiO film in the case where the set including thestep of supplying the chlorosilane-based gas to the wafer 200 and thestep of supplying the N- and H-containing gas to the wafer 200 isperformed a predetermined number of times to form the SiN film over thewafer 200 and the SiN film is oxidized to be changed into the SiO film.As illustrated in FIG. 7B, the present disclosers have confirmed thatwhen the SiON film before the oxidation has a tensile stress having amagnitude of about 0.5 GPa, the stress of the SiO film obtained byoxidizing the SiON film may be a tensile stress having a magnitude ofabout 0.3 GPa which is smaller than 0.5 GPa. On the other hand, asillustrated in FIG. 8B, the present disclosers have confirmed that whenthe SiN film before the oxidation has a tensile stress having themagnitude of about 0.5 GPa, the stress of the SiO film obtained byoxidizing the SiN film changes from the tensile stress to a compressivestress and the magnitude of the stress may be as large as about 0.5 GPa.In FIGS. 7B and 8B, the tensile stress is represented by “+” and thecompressive stress is represented by “—.” From this point, by using theSiON film as a base film, it is possible to reduce the stress of the SiOfilm obtained by oxidizing the base film, as compared with a case wherethe base film is the SiN film.

After the change of the SiON film to the SiO film by the oxidation iscompleted, the valves 243 c and 243 e are closed to stop the supply ofthe O-containing gas and the H-containing gas into the process chamber201. Then, a gas and the like remaining in the process chamber 201 areremoved from the process chamber 201 (purge) according to the sameprocess procedures as in the purge in the step S1.

As the O-containing gas, it may be possible to use an O₂ gas, an O₃gas), a H₂O gas, a H₂O₂ gas, a N₂O gas, a NO gas, a NO₂ gas, a CO gas, aCO₂ gas, or the like. As the H-containing gas, it may be possible to usea H₂ gas or a deuterium (2 Hz) gas. The ²H₂ gas may be also referred toas a D₂ gas. In this step, the supply of the H-containing gas may not becarried out, and the O-containing gas alone may be supplied as anoxidizing gas. Further, in this step, at least one selected from thegroup of the O-containing gas and the H-containing gas may be suppliedafter being plasma-excited. [Repeating Cycle]

Then, by performing the above-described SiON film formation and SiO filmchange again in this order, a SiON film may be formed over the SiO filmformed over the wafer 200 as a base, as illustrated in FIG. 4C, and theSiON film formed over the SiO film as the base may be changed into a SiOfilm, as illustrated in FIG. 4D. In this way, by performing a cycle aplurality of times (n₂ times, where n₂ is an integer of 2 or more), thecycle including non-simultaneously, that is, alternately withoutsynchronization, performing the SiON film formation and the SiO filmchange, the SiO film having a desired thickness may be formed over thewafer 200. This film becomes a high-purity and dense SiO film containinglittle or no N, which has excellent insulating characteristics and thelike. Further, the SiO film formed by performing the cycle ofnon-simultaneously performing the SiON film formation and the SiO filmchange a plurality of times has a stress smaller than that of a SiO filmhaving the same thickness formed by performing the SiON film formationand the SiO film change one time in this order. Further, theabove-described cycle may not be performed a plurality of times, but maybe performed only one time (n₂=1).

(After-Purge and Returning to Atmospheric Pressure)

After the SiO film having the desired thickness is formed over the wafer200, an inert gas acting as a purge gas is supplied into the processchamber 201 from each of the nozzles 249 a to 249 c and is exhaustedthrough the exhaust port 231 a. Thus, the interior of the processchamber 201 is purged, and a gas and reaction by-products remaining inthe process chamber 201 are removed from the process chamber 201(after-purge). Then, the internal atmosphere of the process chamber 201is substituted with an inert gas (inert gas substitution) and theinternal pressure of the process chamber 201 is returned to theatmospheric pressure (returning to atmospheric pressure).

(Boat Unloading and Wafer Discharging)

Then, the seal cap 219 is moved down by the boat elevator 115 to openthe lower end of the manifold 209. Then, the processed wafers 200supported by the boat 217 are unloaded from the lower end of themanifold 209 to the outside of the reaction tube 203 (boat unloading).After the boat unloading, the shutter 219 s is moved and the lower endopening of the manifold 209 is sealed by the shutter 219 s via theO-ring 220 c (shutter close). The processed wafers 200 are unloaded fromthe reaction tube 203 and are discharged from the boat 217 (waferdischarging).

(3) Effects of the Embodiments

According to the embodiments, one or more effects set forth below may beachieved.

(a) By performing a cycle a predetermined number of times, the cycleincluding non-simultaneously performing the SiON film formation and theSiO film change, with the SiON film as the base film, it is possible tosuppress the expansion of the SiO film when the base film is oxidized tobe changed into the SiO film, as compared with a case of performing acycle a predetermined number of times, the cycle includingnon-simultaneously performing the SiN film formation and the SiO filmchange, with the SiN film as the base film. Further, by performing theSiON film formation and the SiO film change in this order, it ispossible to suppress a change in film stress when the base film isoxidized to be changed into the SiO film and to reduce the stress of theSiO film after the base film is changed into the SiO film, as comparedwith a case of performing the SiN film formation and the SiO film changein this order. In this way, according to the embodiments, it is possibleto suppress the “film expansion” and the “change in film stress” beforeand after the oxidation in the SiO film change and provide a SiO filmformed over the wafer 200 with a small internal stress. As a result, itis possible to avoid deformation of an uneven structure such as pillarsformed over the surface of the wafer 200 which is the base when formingthe SiO film.

(b) By performing a cycle a predetermined number of times, the cycleincluding non-simultaneously performing the SiON film formation and theSiO film change, with the SiON film as the base film, it is possible toshorten the time for which the base film is oxidized in the SiO filmchange, as compared with a case of performing a cycle a predeterminednumber of times, the cycle including non-simultaneously performing theSiN film formation and the SiO film change, with the SiN film as thebase film. This makes it possible to improve a productivity of thefilm-forming process.

(c) By performing a cycle a predetermined number of times, the cycleincluding non-simultaneously performing the SiON film formation and theSiO film change, it is possible to provide the SiO film formed over thewafer 200 to contain little or no N and have high purity and excellentinsulating characteristics.

(d) In the SiO film change, by using the O-containing gas+H-containinggas as an oxidizing gas, it is possible to provide the SiO film formedover the wafer 200 to contain little or no N and have high purity andexcellent insulating characteristics. Further, in the SiO film change,since the change of the SiON film to the SiO film by the oxidation canbe efficiently performed, it is possible to increase the productivity ofthe film-forming process.

(e) The above-described effects can be similarly obtained even when theabove-described various silane-based gases, the above-described variousN- and H-containing gases, and the above-described various O-containinggases are used in the SiON film formation, even when the above-describedvarious O-containing gases and the above-described various H-containinggases are used in the SiO film change, or even when the above-describedvarious inert gases are used in each of these steps.

(4) Modifications

The processing sequence in the embodiments may be modified as in thefollowing modifications. These modifications may be used in propercombination. Unless otherwise stated, process procedures and processconditions in each step of each modification may be the same as theprocess procedures and process conditions in each step of theabove-described processing sequence.

(Modification 1)

At least one selected from the group of the O concentration and the Nconcentration of the SiON film formed in the SiON film formation may becontrolled to regulate at least one selected from the group of theexpansion coefficient of the film when the SiON film is changed into theSiO film in the SiO film change and the internal stress of the SiO filmformed in the SiO film change. The O concentration and the Nconcentration of the SiON film can be adjusted by changing at least oneselected from the group of conditions: for example, a type, a partialpressure, a supply flow rate, and a supply time of the O-containing gasand a type, a partial pressure, a supply flow rate, and a supply time ofthe N- and H-containing gas, in the SiON film formation.

This modification also obtains the same effects as the above-describedembodiments. Further, according to the modification, by control of theconcentration of an element (O and/or N) constituting the SiON filmformed in the SiON film formation, not by control of the oxidationcondition in the SiO film change, it is possible to regulate at leastone selected from the group of the expansion coefficient of the filmwhen the SiON film is changed into the SiO film in the SiO film change,and the stress of the SiO film formed in the SiO film change.

(Modification 2)

At least one selected from the group of the O concentration and the Nconcentration of the SiON film formed in the SiON film formation may bechanged every predetermined cycle. The O concentration and the Nconcentration of the SiON film may be regulated every predeterminedcycle by changing, every predetermined cycle, at least one selected fromthe group of conditions: for example, a type, a partial pressure, asupply flow rate, and a supply time of the O-containing gas, and a type,a partial pressure, a supply flow rate, and a supply time of the N- andH-containing gas in the SiON film formation.

This modification also obtains the same effects as the above-describedembodiments. Further, according to the modification, it is possible tochange and regulate a stress of the SiO film, which has a predeterminedthickness formed over the wafer 200, in a thickness direction.

(Modification 3)

The thickness of the SiON film formed in the SiON film formation may bechanged every predetermined cycle. The thickness of the SiON film can beregulated every predetermined cycle by changing, every predeterminedcycle, the number of sets n₁ in the SiON film formation. For example, bymaking the number of sets n₁ in the SiON film formation in a first cycledifferent from the number of sets n₁ in the SiON film formation in atleast one subsequent cycle, the thickness of the SiON film formed in thefirst cycle may be made different from the thickness of the SiON filmformed in the at least one subsequent cycle.

This modification also obtains the same effects as the above-describedembodiments. Further, according to the modification, it is possible tofinely adjust the stress of the SiO film having a predeterminedthickness formed over the wafer 200 in the thickness direction.

(Modification 4)

In the SiON film formation, a set including non-simultaneouslyperforming chlorosilane-based gas supply, O-containing gas supply, andN- and H-containing gas supply in this order may be performed apredetermined number of times (n₁ times, where n₁ is an integer of 1 ormore), as in the gas supply sequence shown below.

[(Chlorosilane-based gas→O-containing gas→N- and H-containing gas)×n₁→O-containing gas+H-containing gas]×n ₂⇒SiO

This modification also obtains the same effects as the above-describedembodiments. Further, according to the modification, since a SiON filmhaving a composition (O concentration and/or N concentration) differentfrom that of the SiON film obtained in the SiON film formation in theabove-described embodiments may be formed in the SiON film formation, itis possible to regulate at least one selected from the group of thecoefficient of expansion of the film in the SiO film change and theinternal stress of the SiO film formed in the SiO film change.

(Modification 5)

Like the processing sequence shown below, a SiO film having apredetermined film thickness may also be formed over a wafer 200 byperforming a cycle a predetermined number of times (n₄ times, where n₄is an integer of 1 or more), the cycle including non-simultaneouslyperforming:

a step of forming a SiN film as a nitride film by supplying achlorosilane-based gas which is a precursor gas, and a N- andH-containing gas which is a nitriding gas, as film-forming gases, to thewafer 200 (SiN film formation); and a step of changing the SiN film intoa SiO film as an oxide film by supplying an O-containing gas and aH-containing gas, as oxidizing gases, to the wafer 200 to oxidize theSiN film (SiO film change).

Further, an oxide film (SiO film) may formed by alternately stacking afirst SiO film having a predetermined film thickness and a second SiOfilm having a predetermined film thickness over the wafer 200 which areformed by performing, a predetermined number of times, a step of formingthe first SiO film by performing a cycle a predetermined number of times(n₂, where n₂ is an integer of 1 or more), the cycle includingnon-simultaneously performing the SiON film formation and the SiO filmchange (first SiO film formation), and a step of forming the second SiOfilm by performing a cycle a predetermined number of times (n₄, where n₄is an integer of 1 or more), the cycle including non-simultaneouslyperforming the SiN film formation and the SiO film change (second SiOfilm formation).

(SiON→Ox)×n ₂→(SiN→Ox)×n ₄→ . . . ⇒SiO

(SiN→Ox)×n ₄→(SiON→Ox)×n ₂→ . . . ⇒SiO

Further, as in the gas supply sequence shown below, in the second SiOfilm formation of this modification, a set including a step of supplyinga chlorosilane-based gas to the wafer 200 and a step of supplying a N-and H-containing gas to the wafer 200 may be performed a predeterminednumber of times (n₃ times, where n₃ is an integer of 1 or more) in theSiN film formation. Process conditions in each step may be the same asthe process conditions in each step in the above-described embodiments.

[(Chlorosilane-based gas→N- and H-containing gas)×n ₃→O-containinggas+H-containing gas]×n ₄⇒SiO

Further, in this modification, the first SiO film formation and thesecond SiO film formation may be performed in the same process chamber201 (in-situ) of the above-described substrate processing apparatus. Theabove-described film-forming gas supply system and oxidizing gas supplysystem may be used both when forming the first SiO film and when formingthe second SiO film. That is, these gas supply systems may be sharedbetween when forming the first SiO film and when forming the second SiOfilm.

This modification also obtains the same effects as the above-describedembodiments. Further, according to the modification, it is possible toregulate, in the thickness direction, the stress of the SiO film formedover the wafer 200, that is, the SiO film formed by alternately stackingthe first SiO film and the second SiO film.

Further, in this modification, the thickness of the first SiO filmhaving a predetermined film thickness may be different from that of thesecond SiO film having a predetermined film thickness. The thickness ofthe first SiO film may be regulated, for example, by varying the numberof sets n₁ in the SiON film formation in the first SiO film formation.Further, the thickness of the second SiO film can be regulated, forexample, by varying the number of sets n₃ in the SiN film formation inthe second SiO film formation. That is, the thicknesses of the first SiOfilm and the second SiO film may be made different from each other bychanging at least one selected from the group of the number of sets n₁and n₃. By making the thicknesses of the first SiO film and the secondSiO film different from each other in this way, it is possible to finelyregulate, in the thickness direction, the stress of the SiO film formedover the wafer 200, that is, the SiO film formed by alternately stackingthe first SiO film and the second SiO film.

Further, in this modification, a film having a tensile stress may beformed as the first SiO film having the predetermined film thickness,and a film having a compressive stress may be formed as the second SiOfilm having the predetermined film thickness. By making the first SiOfilm and the second SiO film have opposite stresses in this way, it ispossible to finely regulate the stress of the SiO film formed over thewafer 200, that is, the SiO film formed by alternately stacking thefirst SiO film and the second SiO film such that the stresses of thefirst SiO film and the second SiO films may be canceled out in thethickness direction. As described with reference to FIGS. 7B and 8B, thepresent disclosers confirmed that the first SiO film tends to have atensile stress and the second SiO film tends to have a compressivestress.

Further, in this modification, of the first SiO film having thepredetermined film thickness and the second SiO film having thepredetermined film thickness, a film having a larger absolute value ofthe film stress may be made thinner than a film having a smallerabsolute value of the film stress. That is, of the first SiO film havingthe predetermined film thickness and the second SiO film having thepredetermined film thickness, the film having the smaller absolute valueof the film stress may be made thicker than the film having the largerabsolute value of the film stress. As described below, such filmthickness regulation may be effective when the first SiO film and thesecond SiO film have opposite film stresses.

In this way, by varying the thicknesses of the first SiO film and thesecond SiO film according to the respective film stresses, it ispossible to finely regulate more appropriately, in the thicknessdirection, the stress of the SiO film formed over the wafer 200, thatis, the SiO film formed by alternately stacking the first SiO film andthe second SiO film (hereinafter also referred to as a stacked SiOfilm). For example, of the first SiO film and the second SiO film, bymaking the film having the larger absolute value of the film stressthinner than the film having the smaller absolute value of the filmstress, it is possible to finely regulate the stress of the stacked SiOfilm formed over the wafer 200 such that a degree of film stress of thefilm having the larger absolute value of the film stress may decrease.Further, for example, of the first SiO film and the second SiO film, bymaking the film having the smaller absolute value of the film stressthicker than the film having the larger absolute value of the filmstress, it is possible to finely regulate the stress of the stacked SiOfilm formed over the wafer 200 such that a degree of film stress of thefilm having the smaller absolute value of the film stress may increase.

As described above with reference to FIGS. 7B and 8B, the presentinventors confirmed that an absolute value of the compressive stress ofthe second SiO film may be larger than an absolute value of the tensilestress of the first SiO film. In this case, by making the second SiOfilm having the predetermined film thickness thinner than the first SiOfilm having the predetermined film thickness, it is possible to finelyregulate the stress of the stacked SiO film formed over the wafer 200such that the stresses of the first SiO film and the second SiO film arecanceled out more appropriately in the thickness direction. For example,it is possible to alleviate the tendency of the stress of the stackedSiO film to be biased toward the compressive stress. Further, in a casewhere the first SiO film and the second SiO film have opposite filmstresses and different absolute values of the respective film stresses,the SiO film having a smaller absolute value of the film stress may bemade thicker than the SiO film having a larger absolute value of thefilm stress in some embodiments. That is, the SiO film having the largerabsolute value of the film stress may be made thinner than the SiO filmhaving the smaller absolute value of the film stress in someembodiments.

Further, in this modification, a set including: a step of forming thefilm having the smaller absolute value of the film stress; a step offorming the film having the larger absolute value of the film stress;and a step of forming the film having the smaller absolute value of thefilm stress of the first SiO film having the predetermined filmthickness and the second SiO film having the predetermined filmthickness may be performed a predetermined number of times. Further,regulation of such a stacking order is further effective when the firstSiO film and the second SiO film have opposite film stresses.

As described above, by regulating the stacking order of the first SiOfilm and the second SiO film according to the film stress, a stackedstructure in which the film having the larger absolute value of the filmstress is sandwiched from both sides by the films having the smallerabsolute value of the film stress may be formed, whereby it is possibleto finely regulate the stress of the stacked SiO film formed over thewafer 200 such that the stresses of the respective SiO film are canceledout in the thickness direction more appropriately.

For example, in a case where the absolute value of the film stress (forexample, compressive stress) of the second SiO film is larger than theabsolute value of the film stress (for example, tensile stress) of thefirst SiO film, a set including the first SiO film formation, the secondSiO film formation, and the first SiO film formation may be performed apredetermined number of times, as in the processing sequence shownbelow. In this case, the first SiO film formation and the second SiOfilm formation are alternately performed a plurality of times, and thefirst SiO film formation is performed at the beginning and the end. Inthis case, it is possible to make the structure of the stacked SiO filmsuch that the second SiO film, which may have a relatively largecompressive stress, is sandwiched between the first SiO films which tendto have a relatively small tensile stress. As a result, it is possibleto finely regulate the stresses of the first SiO film and the second SiOfilm such that the stresses are canceled out more appropriately.Therefore, for example, it is possible to alleviate the tendency of thestress of the stacked SiO film to be biased toward the compressivestress in a well-balanced manner. Further, for example, since the stresson a bottom surface side of the stacked SiO film may be made equal tothe stress on a front surface side of the stacked SiO film, it ispossible to appropriately prevent a stress balance of the stacked SiOfilm from being broken.

(SiON→Ox)×n ₂→(SiN→Ox)×n ₄→ . . . →(SiON→Ox)×n ₂⇒SiO

Further, in this modification, a step of forming the film having thesmaller absolute value of the film stress, a step of forming the filmhaving the larger absolute value of the film stress, and a step offorming the film having the smaller absolute value of the film stress ofthe first SiO film having the predetermined film thickness and thesecond SiO film having the predetermined film thickness may be performedin this order. Further, regulation of such a stacking order is furthereffective when the first SiO film and the second SiO film have oppositefilm stresses.

As described above, by regulating the stacking order of the first SiOfilm and the second SiO film according to the film stress, a stackedstructure in which the film having the larger absolute value of the filmstress is sandwiched from both sides by the films having the smallerabsolute value of the film stress may be formed, whereby it is possibleto finely adjust the stress of the stacked SiO film formed over thewafer 200 the stresses of the respective SiO film are canceled out inthe thickness direction more appropriately.

For example, in a case where the absolute value of the film stress (forexample, compressive stress) of the second SiO film is larger than theabsolute value of the film stress (for example, tensile stress) of thefirst SiO film, the first SiO film formation, the second SiO filmformation, and the first SiO film formation may be performed in thisorder, as in the processing sequence shown below. In this case, the sameeffects as in the above-describes case in which the set including thefirst SiO film formation, the second SiO film formation, and the firstSiO film formation is performed a predetermined number of times areobtained.

(SiON→Ox)×n ₂→(SiN→Ox)×n ₄→(SiON→Ox)×n ₂⇒SiO

(Modification 6)

As in the gas supply sequence described below, in the SiON filmformation of the above-described embodiments, a set including a step ofsupplying a first silane-based gas as a first precursor gas to the wafer200, a step of supplying a second silane-based gas as a second precursorgas to the wafer 200, a step of supplying a N- and H-containing gas as anitriding gas to the wafer 200, and a step of supplying an O-containinggas to the wafer 200 may be performed a predetermined number of times(n₁ times, where n₁ is an integer of 1 or more). The first silane-basedgas and the second silane-based gas have different molecular structures,and each of which has characteristics to be described below.

[(First silane-based gas→Second silane-based gas→N- and H-containinggas→O-containing gas)×n ₁→O-containing gas+H-containing gas]×n ₂⇒SiO

Further, as in the gas supply sequence described below, in the SiN filmformation of the above-described modification 5, a set including a stepof supplying a first silane-based gas as a first precursor gas to thewafer 200, a step of supplying a second silane-based gas as a secondprecursor gas to the wafer 200, and a step of supplying a N- andH-containing gas as a nitriding gas to the wafer 200 may be performed apredetermined number of times (n₃ times, where n₃ is an integer of 1 ormore). Further, in this case, the first silane-based gas and the secondsilane-based gas have different molecular structures, and each of whichhas characteristics to be described below.

[(First silane-based gas→Second silane-based gas→N- and H-containinggas)×n ₃→O-containing gas+H-containing gas]×n ₄⇒SiO

In either case, the first silane-based gas and the second silane-basedgas may be supplied from the above-described first precursor gas supplysystem and second precursor gas supply system, respectively.

In these cases, process conditions of the step of supplying the firstsilane-based gas and the step of supplying the second silane-based gasmay be the same as the process conditions in the step 1 of theabove-described embodiments respectively. Further, by setting the supplytime of the first silane-based gas to be equal to or longer than thesupply time of the second silane-based gas, specifically by setting thesupply time of the first silane-based gas to be longer than the supplytime of the second silane-based gas, effects to be described below maybe obtained more sufficiently. Process conditions in the step ofsupplying the N- and H-containing gas and the step of supplying theO-containing gas may be the same as the process conditions in the step 2and the step 3 of the above-described embodiments, respectively.

According to this modification, the same effects as the above-describedembodiments are obtained.

Further, according to this modification, by using two types ofsilane-based gases, a cycle rate (thickness of the SiON layer or the SiNlayer formed per cycle) in the SiON film formation and the SiN filmformation may be made larger than that in a case of using one type ofsilane-based gas, whereby it is possible to increase the productivity ofthe film-forming process.

Further, in this modification, a gas that is more difficult to decompose(more difficult to adsorb or less reactive) than the second silane-basedgas under the same conditions may be used as the first silane-based gas.By selecting the type of gas in this way, it is possible to improve stepcoverage characteristics of the SiON film or SiN film as the base filmformed over the wafer 200, that is, the SiO film obtained by oxidizingthese films, while increasing the cycle rate. For example, by using agas containing one Si atom in one molecule as the first silane-based gasand using a gas containing two or more Si atoms in one molecule as thesecond silane-based gas, it is possible to achieve the aforementionedeffects, that is, it is possible to improve the step coveragecharacteristics while increasing the cycle rate. For example, when aHCDS gas or an OCTS gas is used as the first silane-based gas, a MCSgas, a DCS gas, a TCS gas, a STC gas, a SiF₄ gas, a SiBr₄ gas, a SiI₄gas, or the like may be used as the second silane-based gas.

OTHER EMBODIMENTS OF THE PRESENT DISCLOSURE

The embodiments of the present disclosure have been described above.However, the present disclosure is not limited to the above-describedembodiments, but various modifications may be made without departingfrom the gist thereof.

For example, examples in which the SiON film formation and the SiO filmchange are performed in the same process chamber 201 (in-situ) have beendescribed in the above-described embodiments. However, the SiON filmformation and the SiO film change may be performed in different processchambers (ex-situ). Further, examples in which when a plurality of SiOfilms are stacked over the wafer 200, each SiO film is formed in thesame process chamber 201 (in-situ) have been described in theabove-described embodiments. However, each SiO film may be formed indifferent process chambers (ex-situ).

In a case where a series of processes are performed in-situ, the wafer200 is not exposed to the atmosphere during the processes and the seriesof process may be performed consistently while the wafer 200 is keptunder vacuum, whereby the substrate processing may be performed stably.Further, in a case where some processes are performed ex-situ, aninternal temperature of each process chamber may be set in advance to,for example, a processing temperature in each process or a temperatureclose to the processing temperature, such that a time for which thetemperature is regulated may be shortened, thereby increasing theproduction efficiency.

Further, for example, examples in which the SiO film is formed over thewafer 200 have been described in the above-described embodiments.However, the present disclosure is not limited to the embodiments, butas in the processing sequence described below, the present disclosuremay also be applied to a case in which a metal-based oxide film such asa titanium oxide film (TiO film), an aluminum oxide film (AlO film), ahafnium oxide film (HfO film), and a zirconium oxide film (ZrO film) isformed over the wafer 200. Further, in this case, the same effects asthe above-described embodiments are obtained.

(TiON→Ox)×n ₂⇒TiO

(AlON→Ox)×n ₂⇒AlO

(HfON→Ox)×n ₂⇒HfO

(ZrON→Ox)×n ₂⇒ZrO

(TiON→Ox)×n ₂→(TiN→Ox)×n ₄→ . . . ⇒TiO

(TiN→Ox)×n ₄→(TiON→Ox)×n ₂→ . . . ⇒TiO

(AlON→Ox)×n ₂→(AlN→Ox)×n ₄→ . . . ⇒AlO

(AlN→Ox)×n ₄→(AlON→Ox)×n ₂→ . . . ⇒AlO

(HfON→Ox)×n ₂→(HfN→Ox)×n ₄→ . . . ⇒HfO

(HfN→Ox)×n ₄→(HfON→Ox)×n ₂→ . . . ⇒HfO

(ZrON→Ox)×n ₂→(ZrN→Ox)×n ₄→ . . . ⇒ZrO

(ZrN→Ox)×n ₄→(ZrON→Ox)×n ₂→ . . . ⇒ZrO

Recipes used in each process may be provided individually according toprocessing contents and may be stored in the memory 121 c via atelecommunication line or the external memory 123. Moreover, at thebeginning of each process, the CPU 121 a may properly select anappropriate recipe from the recipes stored in the memory 121 c accordingto the processing contents. Thus, it is possible for a single substrateprocessing apparatus to form films of various types, composition ratios,qualities, and thicknesses with enhanced reproducibility. Further, it ispossible to reduce an operator's burden and to quickly start eachprocess while avoiding an operation error.

The recipes mentioned above are not limited to newly-provided ones butmay be provided, for example, by modifying existing recipes that arealready installed in the substrate processing apparatus. Once therecipes are modified, the modified recipes may be installed in thesubstrate processing apparatus via a telecommunication line or arecording medium storing the recipes. In addition, the existing recipesalready installed in the existing substrate processing apparatus may bedirectly modified by operating the input/output device 122 of thesubstrate processing apparatus.

Examples in which a film is formed by using a batch-type substrateprocessing apparatus capable of processing a plurality of substrates ata time have been described in the above-described embodiments. Thepresent disclosure is not limited to the above-described embodiments,but may be suitably applied, for example, to a case where a film isformed by using a single-wafer type substrate processing apparatusconfigured to process a single substrate or several substrates at atime. In addition, examples in which a film is formed by using asubstrate processing apparatus provided with a hot-wall-type processfurnace have been described in the above-described embodiments. Thepresent disclosure is not limited to the above-described embodiments,but may be suitably applied to a case where a film is formed by using asubstrate processing apparatus provided with a cold-wall-type processfurnace.

Even in the case of using these substrate processing apparatuses, eachprocess may be performed according to the same processing procedures andprocess conditions as those in the above-described embodiments, and thesame effects as the above-described embodiments are achieved.

The above-described embodiments may be used in proper combination. Theprocessing procedures and process conditions used in this case may bethe same as, for example, the processing procedures and processconditions in the above-described embodiments.

According to the present disclosure in some embodiments, it is possibleto improve a film quality of an oxide film formed over a substrate.

While certain embodiments have been described, these embodiments havebeen presented by way of example only, and are not intended to limit thescope of the disclosures. Indeed, the embodiments described herein maybe embodied in a variety of other forms. Furthermore, various omissions,substitutions and changes in the form of the embodiments describedherein may be made without departing from the spirit of the disclosures.The accompanying claims and their equivalents are intended to cover suchforms or modifications as would fall within the scope and spirit of thedisclosures.

What is claimed is:
 1. A method of processing a substrate, comprising:forming a first film to have a first predetermined film thickness overthe substrate by performing a first cycle a first predetermined numberof times, the first cycle including: (a1) forming an oxynitride film bysupplying a first film-forming gas to the substrate, the oxynitride filmnot containing carbon; and (a2) changing the oxynitride film into afirst oxide film by supplying a first oxidizing gas to the substrate tooxidize the oxynitride film.
 2. The method of claim 1, wherein at leastone selected from the group of a film expansion coefficient whenchanging the oxynitride film into the first oxide film in (a2) and afilm stress of the first oxide film formed in (a2) is regulated bycontrolling at least one selected from the group of an oxygenconcentration of the oxynitride film formed in (a1) and a nitrogenconcentration of the oxynitride film formed in (a1).
 3. The method ofclaim 1, wherein at least one selected from the group of an oxygenconcentration of the oxynitride film formed in (a1) and a nitrogenconcentration of the oxynitride film formed in (a1) is changed wheneverthe first cycle is performed a second predetermined number of times. 4.The method of claim 1, wherein a thickness of the oxynitride film formedin (a1) is changed whenever the first cycle is performed a secondpredetermined number of times.
 5. The method of claim 1, furthercomprising: forming a second film to have a second predetermined filmthickness over the substrate by performing a second cycle a secondpredetermined number of times, the second cycle including: (b1) forminga nitride film by supplying a second film-forming gas to the substrate;and (b2) changing the nitride film into a second oxide film by supplyinga second oxidizing gas to the substrate to oxidize the nitride film,wherein an oxide film formed by stacking the first film and the secondfilm is formed over the substrate by performing the act of forming thefirst film and the act of forming the second film a third predeterminednumber of times.
 6. The method of claim 5, wherein the first film andthe second film have thicknesses different from each other.
 7. Themethod of claim 5, wherein a film stress of the first film is a tensilestress, and wherein a film stress of the second film is a compressivestress.
 8. The method of claim 5, wherein an absolute value of a filmstress of one film of the first film and the second film is larger thanan absolute value of a film stress of the other film of the first filmand the second film, and wherein a thickness of the one film is smallerthan a thickness of the other film.
 9. The method of claim 5, furthercomprising performing a set a fourth predetermined number of times, theset including performing: forming one film of the first film and thesecond film; forming the other film of the first film and the secondfilm; and forming the one film of the first film and the second film,wherein an absolute value of a film stress of the one film is smallerthan an absolute value of a film stress of the other film.
 10. Themethod of claim 5, further comprising sequentially performing: formingone film of the first film and the second film; forming the other filmof the first film and the second film; and forming the one film of thefirst film and the second film, wherein an absolute value of a filmstress of the one film is smaller than an absolute value of a filmstress of the other film.
 11. The method of claim 1, wherein (a1)includes performing a set a second predetermined number of times, theset including performing: supplying a precursor gas as the firstfilm-forming gas to the substrate; supplying a nitriding gas as thefirst film-forming gas to the substrate; and supplying an oxidizing gasas the first film-forming gas to the substrate.
 12. The method of claim11, wherein the act of supplying the precursor gas includes: supplying afirst precursor gas as the precursor gas to the substrate; and supplyinga second precursor gas as the precursor gas to the substrate.
 13. Themethod of claim 5, wherein (b1) includes performing a set a fourthpredetermined number of times, the set including performing: supplying aprecursor gas as the second film-forming gas to the substrate; andsupplying a nitriding gas as the second film-forming gas to thesubstrate.
 14. The method of claim 13, wherein the act of supplying theprecursor gas includes: supplying a first precursor gas as the precursorgas to the substrate; and supplying a second precursor gas as theprecursor gas to the substrate.
 15. The method of claim 12, wherein thefirst precursor gas is more difficult to decompose than the secondprecursor gas under same conditions.
 16. The method of claim 12, whereinthe first precursor gas contains one silicon atom in one molecule, andthe second precursor gas contains two or more silicon atoms in onemolecule.
 17. The method of claim 5, wherein the act of forming thefirst film and the act of forming the second film are performed in thesame process chamber.
 18. The method of claim 5, wherein the act offorming the first film and the act of forming the second film areperformed in different process chambers.
 19. A substrate processingapparatus comprising: a first film-forming gas supply system configuredto supply a first film-forming gas to a substrate; a first oxidizing gassupply system configured to supply a first oxidizing gas to thesubstrate; and a controller configured to be capable of controlling thefirst film-forming gas supply system and the first oxidizing gas supplysystem to perform a process of forming a first film to have a firstpredetermined film thickness over the substrate by performing a firstcycle a first predetermined number of times, the first cycle including:(a1) forming an oxynitride film by supplying the first film-forming gasto the substrate, the oxynitride film not containing carbon; and (a2)changing the oxynitride film into a first oxide film by supplying thefirst oxidizing gas to the substrate to oxidize the oxynitride film. 20.A non-transitory computer-readable recording medium storing a programthat causes, by a computer, a substrate processing apparatus to performa process including: forming a first film to have a first predeterminedfilm thickness over a substrate by performing a first cycle a firstpredetermined number of times, the first cycle including: (a1) formingan oxynitride film by supplying a first film-forming gas to thesubstrate, the oxynitride film not containing carbon; and (a2) changingthe oxynitride film into a first oxide film by supplying a firstoxidizing gas to the substrate to oxidize the oxynitride film.
 21. Amethod of manufacturing a semiconductor device comprising the method ofclaim 1.